Atkins / Paula

Physical Chemistry, 8th Edition

Chapter 16.
Statistical thermodynamics 1:
the concepts

The distribution of molecular states

16.1 Configurations and weights
16.2 The molecular partition function

The internal energy and the entropy

16.3 The internal energy
16.4 The statistical entropy

The canonical partition function

16.5 The canonical ensemble
16.6 The thermodynamic information in the partition function
16.7 Independent molecules
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Statistical Thermodynamics: Concepts

Statistical thermodynamics -- link between microscopic
properties of matter and its bulk properties.
Two key ideas: Boltzmann distribution predicts populations of
states in systems at thermal equilibrium. Its derivation in terms
of the distribution of particles over available states.
The derivation leads naturally to the introduction of partition
function, the central mathematical concept of Ch.16, 17.
How to interpret partition function and calculate it in simple
cases.
How to extract thermodynamic information from the partition
function
Generalize to include systems that are composed of assemblies
of interacting particles. Very similar equations but much more
widely applicable.

The distribution of molecular states

System composed of N molecules. Although the total energy is constant at

E, it is not possible to be definite about how that energy is shared between
the molecules. Collisions result in the ceaseless redistribution of energy not
only between the molecules but also among their different modes of motion.
Population of a state, the average number of molecules that occupy it, on
average there are ni molecules in a state of energy i. The populations of the
states remain almost constant, but the precise identities of the molecules in
each state may change at every collision.
In this section is the calculation of the populations of states for any type of
molecule in any mode of motion at any temperature. The only restriction is
that the molecules should be independent, the total energy of the system is
a sum of their individual energies.
Principle of equal a priori probabilities, the assumption that all
possibilities for the distribution of energy are equally probable. A priori
means in this context loosely as far as one knows.
The populations of states depend only on the temperature. That is,
statistical thermodynamics provides a molecular justification for the
concept of temperature and some insight into this crucially important
quantity.

16.1 Configurations
and weights
(a) Instantaneous
configurations
Eq.(16.1):

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Chapter 16. Statistical thermodynamics 1: the concepts

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Stirlings approximation

16.1Configurations and weights

(b) The Boltzmann distribution

Boltzmann distribution:

where T is the thermodynamic temperature and k is

Boltzmanns constant. The thermodynamic temperature is
the unique parameter that governs the most probable
populations of states of a system at thermal equilibrium.

16.2 The molecular partition function

Boltzmann distribution
where pi is the fraction of molecules in the state i, pi =
ni/N, and q is the molecular partition function:

If, e.g., gi states have the same energy i (so the level is
gi-fold degenerate),

where the sum is now over energy levels (sets of states

with the same energy), not individual states.

Ex. 16.1 Writing a partition function

Write partition function of a linear molecule (such as HCl) treated as a rigid

rotor.
Method: Use eqn 16.9 (a) energies of levels, (b) degeneracies. The energies
of levels relative to 0 for the lowest energy state. Energy levels of rigid linear
rotor Sect. 13-5c.
Answer: Eqn 13.31, energy levels of a linear rotor: hcBJ(J + 1), with J = 0,
1, 2, . . . . with degeneracy: 2J + 1

Solve numerically from B (spectroscopy or calculation) and T. [Sect. 17-2b,

unsymmetrical linear rotors (for instance, HCl, not CO2)]

Test 16.2 Partition function for a two-level system, the lower state (at energy
0) being nondegenerate, the upper state (at an energy ) doubly degenerate.
Correct Answer: q = 1 + 2e

16.2(a) An interpretation of the partition function

The molecular partition function gives an indication of the

number of states that are thermally accessible to a
molecule at the temperature of the system.
At T = 0,only the ground level is accessible and q = g0.
At very high temperatures, virtually all states are
accessible, and q is correspondingly large.

Ex.16.2 Evaluating the

partition function for a
uniform ladder of energy
levels
Evaluate the partition
function for a molecule
with an infinite number
of equally spaced
nondegenerate energy
levels (Fig. 16.3). These
levels can be thought of
as the vibrational energy
levels of a diatomic
molecule in the harmonic
approximation.
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Method: eqn 16.8:

Answer: If the separation of

neighbouring levels is , the partition
function is

q rises from 1 to infinity as the

temperature is raised.

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Test 16.3 Find and plot the partition function of a system with one
state at zero energy and another state at energy .

Answer: q = 1 + e, Fig. 16.5

From eqn 16.8 and q in Ex. 16.2 for a
uniform ladder of states of spacing , (16.12)
The fraction of molecules in the state with
energy i is (16.13)

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2-level system in Test 16.3:

(Eq.16.14)

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Chapter 16. Statistical thermodynamics 1: the concepts

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Ex. 16.3 Using the partition function to calculate a population

Calculate the proportion of I2 molecules in their ground, first excited, and

second excited vibrational states at 25C. The vibrational wavenumber is
214.6 cm1.
Method Vibrational energy levels have a constant separation (in the harmonic
approx., Sect. 13-9), so the partition function is given by eqn 16.12 and the
populations by eqn 16.13. To use the latter equation, identify the index i with
the quantum number v, and calculate pv for v = 0,1, and 2. At 298.15 K, kT/hc
= 207.226 cm1.
Answer

from eqn 16.13 that the populations

Therefore, p0 = 0.645, p1 = 0.229,p2 = 0.081. The I-I bond is not stiff and the
atoms are heavy: as a result, the vibrational energy separations are small and
at room temperature several vibrational levels are significantly populated. The
value of the partition function, q = 1.55, reflects this small but significant
spread of populations.

Bose-Einstein States: Low Temperatures

In optical trapping, atoms in the gas phase are cooled by inelastic

collisions with photons from intense laser beams, which act as walls of a
very small container.
Adiabatic demagnetization: in the absence of a magnetic field, the
unpaired electrons of a paramagnetic material are orientated at random; in
the presence of a magnetic field there are more spins (ms = 1/2) than
spins (ms = +1/2).
The application of a magnetic field lowers the entropy of a sample and, at
a given temperature, the entropy of a sample is lower when the field is on
than when it is off. Even lower temperatures can be reached if nuclear
spins (which also behave like small magnets) are used instead of electron
spins in the technique of adiabatic nuclear demagnetization, which has
been used to cool a sample of silver to about 280 pK.
In certain circumstances it is possible to achieve negative temperatures,
and the equations derived later in this chapter can be extended to T <0
with interesting consequences (Further info 16.3).

Adiabatic demagnetization cools sample

1) Paramagnetic d/f metal complex sample surrounded
by helium (provides thermal contact with cold
reservoir) cooled to ~1K, then exposed to strong
magnetic field. AB - isothermal, and energy leaves the
system as heat while the electron spins adopt the lower
energy state; 2) pump away the helium, and reduce the
magnetic field to zero - adiabatic and effectively
reversible - B to C. Lower entropy in the absence of a
magnetic field corresponds to a lower temperature.

Chapter 16. Statistical thermodynamics 1: the concepts

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Approximations and factorizations

The partition function for a particle in a one-dimensional box
Energy levels of a molecule of mass m in a container of length X are (eq.9.4a)
with L = X:

The lowest level (n = 1) has energy h2/8mX2, energies relative to that level are

The sum to evaluate

The translational energy levels are very close together in a container the size of a
typical laboratory vessel; the sum can be approximated by an integral:

Extending lower limit to n = 0 and replacing of n2 1 by n2 introduces negligible

error. Substitute x2 = n2, dn = dx/()1/2,

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If the energy is a sum of contributions from independent modes of

motion, then the partition function is a product of partition functions
for each mode of motion.
Molecule free to move in 3-D. Y - length of the container in y-dir, Z
- in z-dir. The total energy of a molecule is the sum of its
translational energies in all 3 directions:

- thermal wavelength
(thermal de Broglie
wavelength) of the
molecule
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Illus 16.3 Calculating the translational partition function

Translational partition function of H2 molecule confined to 100 cm3 vessel at 25C m = 2.016 u

1 J = 1 kg m2 s2

About 1026 quantum states are thermally accessible, even at room temperature and for this light
molecule. Many states are occupied if the thermal wavelength (71.2 pm) is small compared with
the linear dimensions of the container.
Test 16.5 Calculate the translational partition function for a D2 molecule under the same
conditions.
Correct Answer q = 7.8 1026 , 23/2 times larger

The average separation of the particles in the container, d. Because q is the total
number of accessible states, the average number of states per molecule is q/N. For this
quantity to be large, we require V/N3>>1. However, V/N is the volume occupied by a
single particle, and therefore the average separation of the particles is d = (V/N)1/3. The
condition for there being many states available per molecule is therefore d3/3 >>1, and
therefore d >>. That is, for eqn 16.19 to be valid, the average separation of the
particles must be much greater than their thermal wavelength. For H2 molecules at 1
bar and 298 K, the average separation is 3 nm, which is significantly larger than their
thermal wavelength (71.2 pm).

The internal energy and the entropy

The importance of the molecular partition
function is that it contains all the
information needed to calculate the
thermodynamic properties of a system of
independent particles. In this respect, q
plays a role in statistical thermodynamics
very similar to that played by the
wavefunction in quantum mechanics: q is a
kind of thermal wavefunction.

16.3 The internal energy

(a) The relation between U and q

The total energy of the system relative to the energy of the lowest state

Because the most probable configuration is so strongly dominating, use the

Boltzmann distribution for the populations

A form involving only q

Illust 16.4 The energy of a two-level system

2-level partition function q = 1 + e, the
total energy of N two-level systems is

The energy is zero at T = 0, when only the lower state

(at the zero of energy) is occupied, and rises to N
as T , when the two levels become equally
populated.

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(a) The relation between U and q (contd)

(b) The value of

Justif. 16.3 The internal energy of a perfect gas

(b) The value of (contd)

equipartition expression for the internal energy of a monatomic perfect gas,

which from Molecular interpretation 2.2

Further Info 16.2 The Boltzmann formula

A change in the internal energy

(16.51)
may arise from either a modification of the energy levels of a system (when i
changes to i + di) or from a modification of the populations (when ni
changes to ni + dni). The most general change is therefore

(16.52)
Because the energy levels do not change when a system is heated at
constant volume (Fig. 16.18), in the absence of all changes other than
heating

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From thermodynamics (eqn 3.43) under the same conditions

For changes in the most probable configuration (the only one we need
consider), rearrange eqn 16.49

As the number of molecules is constant, the sum over dni =0

This relation strongly suggests the definition S = k ln W, as in eqn 16.34.

16.4 The statistical entropy

If it is true that the partition function contains all thermodynamic information, then
it must be possible to use it to calculate the entropy as well as the internal energy.
From Sect 3-2 entropy is related to the dispersal of energy and that the partition
function is a measure of the number of thermally accessible states, we can be
confident that the two are indeed related.
1) Boltzmann formula for the entropy:
(16.34)
W is the weight of the most probable configuration of the system.
2) Express W in terms of the partition function.
The statistical entropy behaves in exactly the same way as the thermodynamic
entropy. As the temperature is lowered, the value of W, and hence of S, decreases
because fewer configurations are compatible with the total energy. In the limit T
0, W = 1, so ln W = 0, because only one configuration (every molecule in the
lowest level) is compatible with E = 0. It follows that S 0 as T 0, the Third
Law of thermodynamics, that the entropies of all perfect crystals approach the
same value as T 0 (Section 3-4)
Relate the Boltzmann formula for the entropy to the partition function. Substitute
the expression for ln W in eqn 16.3 into eqn 16.34

Justification 16.4 The statistical entropy

eqn 16.3 (ln W = N ln N i ni ln ni) and N = ini

where pi = ni/N, the fraction of molecules in state i. From

eqn 16.7

the sum over the pi is equal to 1 and (from eqn 16.27, 16.30)

= 1/kT, so eqn 16.35 immediately follows.

Ex.16.4 Calculating the entropy of a collection of oscillators

Calculate the entropy of a collection of N independent harmonic

oscillators, using vibrational data for I2 vapor at 25C (Ex.16.3).
Method To use eqn 16.35, we use the partition function for a molecule
with evenly spaced vibrational energy levels, eqn 16.12. With the
partition function available, the internal energy can be found by
differentiation (as in eqn 16.31a), and the two expressions then
combined to give S.
Answer The molecular partition function as given in eqn 16.12 is

The internal energy is obtained by using eqn 16.31a:

This function is plotted in

Fig. 16.12. For I2 at 25C,
= 1.036 (Ex.16.3), so Sm
= 8.38 J K1 mol1.

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Test 16.6 Evaluate

the molar entropy
of N 2-level
systems and plot
the resulting
expression. What is
the entropy when
the two states are
equally thermally
accessible?

Answer:
S/Nk = /(1 + e) + ln(1 + e);
S = Nk ln 2

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The canonical partition function

generalize our conclusions to include systems
composed of interacting molecules.
how to obtain the molecular partition function
from the more general form of the partition
function developed here.
16.5 The canonical ensemble
The crucial new concept we need when treating
systems of interacting particles is the ensemble.
Like so many scientific terms, the term has
basically its normal meaning of collection

(a) The concept of ensemble

Closed system of specified V, composition, and T,
and think of it as replicated times. All the
identical closed systems are regarded as being
in thermal contact with one another, so they
can exchange energy. The total energy of all
the systems is and they are in thermal
equilibrium with one another, have the same T.
This imaginary collection of replications of the
actual system with a common temperature is
called the canonical ensemble.

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(a) The concept of ensemble

Canon - according to a rule. Microcanonical ensemble the

condition of constant T is replaced by the requirement that all
the systems should have exactly the same energy: each system
is individually isolated.
Grand canonical ensemble: V, T of each open system is the
same. Matter can be imagined as able to pass between the
systems; the composition of each one may fluctuate, but the
chemical potential is the same in each system:
Microcanonical ensemble: N, V, E common
Canonical ensemble: N, V, T common
Grand canonical ensemble: , V, T common

An ensemble is a collection of imaginary replications of the system, so we

are free to let the number of members be as large as we like; when
appropriate, we can let become infinite. The number of members of the
ensemble in a state with energy Ei is denoted i, and we can speak of the
configuration of the ensemble (by analogy with the configuration of the
system used in Sect 16-1) and its weight, . Note that is unrelated to N,
the number of molecules in the actual system; is the number of imaginary
replications of that system.

(b) Dominating configurations

As in Sect 16-1, some of the configurations of the ensemble will be very

much more probable than others. There will be a dominating configuration,
we can evaluate the thermodynamic properties by taking the average over
the ensemble using that single, most probable, configuration. In the
thermodynamic limit of , this dominating configuration is
overwhelmingly the most probable, and it dominates the properties of the
system virtually completely.
Following the argument in Sect 16-1 with the modification that N and ni are
replaced by and i. The weight of a configuration {0,1,...} is

(16.36)
The configuration of greatest weight, subject to the constraints that the total
energy of the ensemble is constant at and that the total number of
members is fixed at , is given by the canonical distribution:

(16.37)
The quantity Q, which is a function of the temperature, is called the
canonical partition function.

(c) Fluctuations from the most probable distribution

The canonical distribution in eqn 16.37 is only apparently an
exponentially decreasing function of the energy of the system.
We must appreciate that eqn 16.37 gives the probability of
occurrence of members in a single state i of the entire system
of energy Ei. There may in fact be numerous states with
almost identical energies. For example, in a gas the identities
of the molecules moving slowly or quickly can change
without necessarily affecting the total energy. The density of
states, the number of states in an energy range divided by the
width of the range (Fig. 16.15), is a very sharply increasing
function of energy. It follows that the probability of a member
of an ensemble having a specified energy (as distinct from
being in a specified state) is given by eqn 16.37, a sharply
decreasing function, multiplied by a sharply increasing
function (Fig. 16.16). Therefore, the overall distribution is a
sharply peaked function. We conclude that most members of
the ensemble have an energy very close to the mean value.

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16.6 The thermodynamic information in the partition function

Like the molecular partition function, the canonical partition function

carries all the thermodynamic information about a system. However, Q is
more general than q because it does not assume that the molecules are
independent. Use Q to discuss the properties of condensed phases and real
gases where molecular interactions are important.
(a) The internal energy
If the total energy of the ensemble is , and there are members, the
average energy of a member is E = /. The internal energy of the system
in the limit of (and ) approaching infinity:

(16.38)
The fraction, i,of members of the ensemble in a state i with energy Ei is
given by the analogue of eqn 16.7 as

(b) The entropy

The total weight, , of a configuration of the
ensemble is the product of the average
weight W of each member of the ensemble,
= W. Hence,
(16.42)
By the same argument used in Sect. 16-4,

16.7 Independent molecules

We shall now see how to recover the
molecular partition function from the more
general canonical partition function when
the molecules are independent. When the
molecules are independent and
distinguishable (in the sense to be
described), the relation between Q and q is

Justification 16.5 The relation between Q and q

The total energy of a collection of N independent molecules is the sum of

the energies of the molecules. Therefore, the total energy of a state i of the
system

In this expression, i(1) is the energy of molecule 1 when the system is in

the state i,i(2) the energy of molecule 2 when the system is in the same
state i, and so on. The canonical partition function is then

The sum over the states of the system can be reproduced by letting each
molecule enter all its own individual states. Therefore, instead of summing
over the states i of the system, we can sum over all the individual states i of
molecule 1, all the states i of molecule 2, and so on. This rewriting of the
original expression leads to

(a) Distinguishable and indistinguishable molecules

Justification 16.6 The SackurTetrode equation

For a gas of independent molecules, Q may be replaced by qN/N!, with

the result that eqn 16.43 becomes

Because the number of molecules (N = nNA ) in a typical sample is large,

use Stirlings approximation (eqn 16.2)

The only mode of motion for a gas of atoms is translation, and the
partition function is q = V/3 (eqn 16.19), where is the thermal
wavelength. The internal energy is given by eqn 16.32, so the entropy is

which rearranges into eqn 16.46.

(b) The entropy of a monatomic gas

An important application of the previous material is the
derivation of the SackurTetrode equation for the entropy
of a monatomic gas:

(16.46a)
This equation implies that the molar entropy of a perfect
gas of high molar mass is greater than one of low molar
mass under the same conditions (because the former has
more thermally accessible translational states). Because the
gas is perfect, we can use the relation V = nRT/p to express
the entropy in terms of the pressure as

Ex 16.5 Using the SackurTetrode equation

Calculate the standard molar entropy of gaseous argon at 25C.

Method To calculate the molar entropy, Sm, from eqn 16.46b, divide both
sides by n. To calculate the standard molar entropy, S m, set p = p in the
expression for Sm:

Answer The mass of an Ar atom is m = 39.95 u. At 25C, its thermal

wavelength is 16.0 pm (by the same kind of calculation as in Illust16.3),

We can anticipate, on the basis of the number of accessible states for a

lighter molecule, that the standard molar entropy of Ne is likely to be
smaller than for Ar; its actual value is 17.60R at 298 K.
Test 16.7 Calculate the translational contribution to the standard molar
entropy of H2 at 25C.
Answer: 14.2R

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